Resinous condensation products from an aldehyde or a ketone and an n-alkenylarylamine



Patented Jan. 31, 1950 RESINOUS CONDENSATION PRODUCTS FROM AN ALDEHYDEOR A KETONE AND AN N-ALKENYLARYLAMINE Joseph D. Danforth, Grinnell,Iowa, assignor to Universal Oil Products Company, Chicago, Ill., acorporation of Delaware No Drawing. Application February 16, 1948,Serial No. 8,753

22 Claims. (Cl. 2.6072.5)

1 This application is a continuation in part of my application SerialNo. 658,205, filed March 28, 1946 and now abandoned.

The present invention relates to a process for the manufacture ofresinous condensation prod-- nets and to a new class of such productscomprising the condensates formed by reacting a particular class ofarylamines, with organic compounds containing a carbonyl group andselected from the aldehydes and ketones. More particularly the inventionconcerns a new class of resinous products characterized as thecondensates of N-alkenylarylamines with a carbonyl reactant selectedfrom the group of compounds characterized as aldehydes and ketonesincluding the aliphatic and cyclic members of such series, the cyclicmembers thereof comprising the naphthenic, aromatic and heterocyclicaldehydes and ketones. It is thus one object of the invention to prepareresinous materials containing alkylene substituted nitrogen groups.

A further object of this invention is to prepare a new class ofresin-like products useful as accelerators in the vulcanization ofrubber, as valuable additives in the manufacture of plastics, and asbodying materials in the production of drying oils, paints andvarnishes.

In its broad aspects the present invention relates to a process for theproduction of a resinous product which comprises reacting analkenylarylamine with an organic compound containing a carbonyl radicalselected from thegroup consisting of the aldehydes and ketones atcondensation reaction conditions.

A more specific embodiment of the present process for the production ofresin-like condensates of wholly organic composition is represented' byreacting equimolecular proportions of crotonaldehyde andN-butenylaniline at a temperature of from about to about 35 C. andseparating the" resultant resinous product by mixing the resultingreaction mixture with water.

In another embodiment of the invention the reaction of a carbonylreactant and an alkenylarylamine is carried out in the presence ofanacidic catalyst to yield thereby a solid resinous product havingthermoplastic properties.

Other specific embodiments relating to specified reactants and toprocedures employed in effecting the condensation reaction andseparation of the product will be described in greater detail in thefollowing further description of the process.

. It is generally known that primary arylamlnes,

with compounds containing a carbonyl radical such as aldehydes toproduce resin-like materials, the properties of which are dependent uponthe specific reactants employed in the condensation reaction by whichsuch resins are formed. According to the present invention I havediscovered that new and distinctive products ranging 'in physicalproperties from viscous liquids to hard brittle solid resinous productsmay be prepared from certain classes of the above reactants comprisingan aldehyde and/or a ketone as one reactive component and anN-alkenylarylamine as the second reactive component.

The class of compounds herein referred to as the N-alkenylarylamines'are defined structurally as the aromatic secondary amines and moreparticularly characterized as compounds containing an aromatic nucleussubstituted on one of its nuclear positions by an amino radical havingattached thereto on the nitrogen atom, an alkenyl group having thegeneral formula: CnH21i-1, said latter alkenyl group representing theradical ob-- tained by removal of two hydrogen atoms from thecorresponding alkyl group. The members of this class of amine may bereadily and convenientIy prepared by the direct substitution of thealkenyl group into the amino radical of an arcmatic amine. The presentalkenylarylamlne may be prepared for example, by reacting a conjugateddiolefinic hydrocarbon containing the same number of carbon atoms permolecule as the alkenyl radical attached to the amino group herein, andthese maybe synthesized by means recognized by the art other than theabove condensation-type reaction between a diolefln and such as aniline,react under certain conditions a primary aromatic amine. The primaryaromatic amines utilizable in the preparation of the N-alkenylarylaminesaccording to the process described above include the mono-aminocompounds such as aniline and nuclearly substituted anilines, such astoluidine, xylidine, etc. The reaction involved in the preparation ofthe alkenylarylamine by the condensation of a diolefinic hydrocarbonwith an aryiamine is usually conducted at a temperature within the rangeof from about 100 to about 150' 0.. although the conditions ofpreparation may vary in the case of certain reactants which requirehigher or lower reaction temperatures. Usually, an equimoiecularproportion of the reactants is utilized in the preparation, since higherproportions of the diene in the reaction or additional quantities of thediene added subsequently to the formation of the monoalkenylarylaminecontaminate the latter desired product with N,N'-dialkenylarylaminecorresponding approximately to the excess of the diene added to thereaction mixture.

The reactant characterised herein as an organic compound containing acarbonyl radical selected from the group consisting of the aldehydes andketones, which when contacted with the N-alkenylarylamine at reactionconditions forms the resinous product of this invention, may

be selected from thelarge number of aldehydes and ketones comprising thealiphatic saturated or unsaturated compounds, either of straightorbranched-chain configuration, the aliphatic aldehyde polymers. and thecyclic members oi the broad classification oi carbonyl compounds, eitherof heterocyclic or homocyclic structure, including the aromatic, as wellas naphthenic or saturated cyclic series. Polycarbonyl reactants or amixture of one or more of aldehydes and/or a ketones of the aboveclasses may also be utilized in the condensation type of reaction.Typical examples of each of the above classes of aldehydes and ketonesare given in the following table, although the compounds named in thetable are not to be interpreted as restricting the scope of theinvention to the specific members of each series named therein:

I YJi-o-BY.

where R, Y and n have the same designation as that specified above forthe substituted aldehydes. I

The reaction of the present process whereby a resinous product is formedis preferably effected in the presence of a catalytic substance of knowncapacity for catalyzing condensation reactions. Among said group ofcondensation catalysts the aromatic acids, such as benzoic acid oraliphatic acids such as glacial acetic or oxalic acid and variousmineral acids, such as hydrochloric, suliuric and phosphoric acids, arevery effective in initiating and accelerating the condensation reactionof the present process. The catalyst may be subsequently removed fromthe resinous product by treating the latter with a solvent whichselectively dissolves the acid from the resin, such as water, alcohols,etc. Although the condensation reaction here involved is preferablyconducted in the presence of a catalyst of the above specified type, itis to be emphasized that catalytic agents are not necessarily requiredin all instances to efiect a given condensation. Thus, certainN-alkenylarylamines, aldehydes and ketones, especially the unsaturatedaliphatic and aromatic aldehydes and ketones containing unsaturatedsubstituted or unsubstituted hydrocar- Ketones simple aldehydes andketones. bonyl compound may contain as substitutents Acetone,mcthylethyl ketone. Methyl vinyl ketonc, ethylidene ace- Aoetoghenone.Oyclo ranone,

TABLE Garbo} 1 compounds utilizable as reactants Aldehydes Aliphatic:

ss ted J'cnnaldehyde, mtg-aldehyde."

Unsaturated. Auoleimcrotonaide yde ehed Chain Isovaleraldch AliphaticPolymer Paralormalde yde omocyclic:

N aphthenic (cyclic saturated)- Pentahydrobcnzaldehyde Ammatio Cinnamicaldehyde Heterocggli Fur-[uni Polycar nyl Glynn] The condensationreaction of the present process may also be obtained by the reaction ofcertain substituted derivatives of the carbonyl reactant to provideresinous products having modified properties difiering in some respectsfrom the products obtained by the condensation of the Thus, thecarattached to carbon atoms other than the carbonyl group one or more ofsuch radicals as halogen, particularly the chloro and bromo members oithis group. hydroxyl. iamino, and carboxyl.

Hie substituted derivatives of the simple aldehydes and ketoncs may berepresented structurally by the general formula:

rf-d-ny. for the aldehydes, in which R. is at least a substituted methylgroup and is selected from the group of substituted hydrocarbon radicalsconsisting of alkyl, 11111.. alkenyl, aralkyl and naph- Beuzoylacetone.

present resinous product. In some instancw, ior example, the reactantsmay be mixed at room temperature or below in the entire absence of thecatalyst and a reaction occurs, as evidenced by the spontaneousliberation of heat the progressive increase in the viscosity of thereaction mixture, and the formation of a distinct resinous product. Thepreferred procedure, however, is to employ a catalyst of the typespecified above, since it has been observed that the catalyzed reactionproceeds at a more rapid rate and the product isolated from the reactionmixture is a material possessing more of the desired resinous propertiesof products oi. this type. Furthermore, it has been observed that it isnot essential in most instances to heat the reaction mixture in order toinitiate the condensation reaction. In utilizing the relatively reactivecarbonyl compounds or N-alkenylarylamines as reactants, the condensationreaction may begin at comparatively low temperatures such as. forexample, at room temperature or from about 25 to 30 C.

thene (cycloalkyl) Y is a substituent of said sub- II by merely mixingthe components in the absence of a catalyzing material, although in thecase of other reactants, catalysts may be added to the reaction mixtureor the mixture of reactants may be heated to somewhat highertemperatures up to about 200 C. to initiate the condensation reaction orcomplete the condensation of partially reacted starting materials.

The product formed in the initial condensation may be isolated byneutralization of the acid catalyst, by mixing, for example, the productwith an aqueous alkali solution or by the addition of water to thereaction mixture, thereby coagulating the resinous product.

It is also within the scope of the present invention to carry out thereaction in the presence of a solvent which is miscible with thereactants and/or the resultant resinous product. The solvent, forexample, may be selected fromthe low molecular weight hydrocarbons, suchas hexane, petroleum ether, etc., the halogen substituted hydrocarbons,such as chloroform, etc., and the lower alcohols and ethers such asethanol, butanol, diethyl ether, etc. The solvent and catalyst functionsmay be combined in a single compound, such as acetic acid, oxalic acid,etc. The

solvent may thereafter be removed from the product by washing with asecondary solvent miscible with the primary solvent or by evaporatingthe solvent .irom the product resin. In many cases it is desirable toemploy the solvent as a diluent of the reactants so as to control therate of reaction or the temperature developed in the reaction mixture,for example, by refluxing the solvent. When such precautions are taken,the product usually has a more desirable color and other physicalproperties are improved such as hardness etc.

After completion of the initial condensation reaction and the separationof the product from the reaction mixture, the product may be dried andpulverized into a finely divided form suitable for subsequent moldingoperations, mixing into plastics or protective covering compositions, orfor storage, as desired. The resinous product formed in the initialreaction may be further reacted with additional quantities of either thesame or a different carbonyl compound than the aldehyde or ketoneemployed in the initial reaction, to form thereby a fully reactedcondensation product which is usually harder and more refractory thanthe initial partial condensation product. In general, the utilization ofan excess of the N- alkenylarylamine, for example a ratio thereof to thealdehyde greater than a 2:1 molecular ratio, results in the productionof a softer resinous product. As the proportion of aldehyde to amineincreases in the initial reaction mixture, the resultant product tendsto be progressively harder and tougher, so that a condensate initiallyformed from a mixture of reactants containing less aldehyde than the 2:1ratio of amine to aldehyde may be subsequently hardened by furtherincorporating into the initial reaction product additional aldehyde andthereafter reacting the latter mixture to form the hardened product.

The N-alkenylarylamine-aldehyde and/or ketone condensation productsformed according to the present process are usually resinous, varying inhardness from soft, pliable masses to hard solids which may be tough orbrittle, depending upon the reactants and vary in lustre from solidshaving a. glossy surface to dull, lustreless resins. The physicalproperties of the product depend principally upon the reactants utilizedand their effect on the molecular weight of the product as well as theuse of a catalyst in the reaction.

The products have a widespread utility in various arts, depending in alarge measure upon the physical properties of the resin. Since thepresent products have unsaturated linkages in their molecular structure,they may be incorporated into drying oils and as such are also subjectto polymerization and oxidation reactions which take place during theso-called drying" process. When compounded with other drying oils of theglyceride type, for example, certain of the present resins, especiallythe solid resinous products, give valuable film-forming and bodyingproperties to paints and varnishes in which these resins areincorporated. varnishes are obtained from these products which dryquickly and completely and yield a glossy surface resistant tochemicals, water and abrasive agents. In some cases the present productsare valuable vulcanization accelerators, and others, when incorporatedinto synthetic or natural rubbers, retard the deterioration andoxidation of the rubber composition. In addition to their value asadditives in other compositions, the present products are in some casesvaluable as resins per se in forming molded and extruded articles or forimpregnation of ccllulosic materials such as wood chips,

cotton linters, or other fibrous materials to form semi-rigid structuralshapes.

The following examples are presented for the purposes of illustratingthe present process in some of its specific applications, but should notbe construed as restricting the generally broad scope of the invention,either as to the reacting components or as to the reaction conditions.

EXAMPLE I The above N -buten ylaniline was utilized in the followingexamples to prepare the resins hereinafter described, although it is tobe emphasized that other N-alkenylarylamines may be prepared, such asalkenyl derivatives prepared from aromatic amines other than aniline,and other diolefins of higher molecular weight than butadiene; thus, theN -alkenylarylamine may be prepared from such compounds as toluidine andsuch diolefins, as pentadiene, to yield the correspondingN-pentenyltoluidine.

A reddish colored solid resin was obtained by the condensation ofN-butenylaniline, prepared as above, with para-formaldehyde. 14.7 gramsof N-butenylaniline (0.1 mol) was mixed with 3.0 grams ofpara-formaldehyde (0.1 mol equivalent of formaldehyde) in 25 ml. ofglacial acetic acid and the mixture heated gently to about 40 C. Avigorous reaction occurred and a reddish colored solution of the resinin glacial acetic acid was formed. The resin was isolated by dilutingthe reaction mixture with water, thereby causing a coagulation of theresin which separated as a solid product in fine particles.

EXAMPLE :1 5.6 grams of acrolein (0.1 mol) was mixed with 14.! grams ofN-hutenylaniline (0.1 mol). The mixture reacted spontaneously withoutthe addition of heat yielding a viscous condensation product.

A similar mixture in the same molecular proportions was reacted in thepresence of an acid catalyst to yield a hard brittle resin; 14.! gramsof N-butenylaniline was mixed with 2 cc. of 10 N.hydrochlorieackiandthemixturewas addedto 5.8 grams of acrolein.- Themixture reacted vigorously on each addition of the reactants andliberated considerable heat so that cooling was necessary. The finalproduct was added to water to recover a hard brittle resin.

murmur A condensation product of furfuraldehyde and 'N-butenylanilinewas prepared by adding 9.60 grams (0.1 mol) of furfural to a mixture of0.5 gram oxalic acid and 14.7 grams N-butenylaniline. the reactantscombining vigorously with the spontaneous generation of heat. Theresultant resin was poured while molten onto a coolsurfaceandrapidlysolidifledtoahardglossyresinous product.

EXAMPLE IV A resinom tion product is formed by reacting 16.1 grams (0.1mol) of N-pentenylaniline and 13.8 grams (0.1 mol) of phorone at atemperature of approximately 40 C., 0.5 gram of oxalic acid being addedto the mixture as catalyst. The reaction is spontaneous and the mixtureis cooled to maintain the temperature at approximately the above value.The resinous product is a hard thermoplastic material.

I claim as my invention:

l. A process for the production of a resinous product which comprisesreacting an N -aikenylarylamine containing an alkenyl group of at least4 carbon atoms with a carbonyl compound selected from the groupconsisting of the aldehydes. and ketones.

2. The process of claim 1 further characterized in that said carbonylcompound is reacted with said N-alkenylarylamine in the presence of anacidic condensation catalyst.

3. A process for the production of aresinous product which comprisesreacting an N-alkenylarylamine containing an alkenyl group of at least 4carbon atoms and of the general formula: CsHIa-i with a carbonylcompound selected from the group consisting of the aldehydes, andketones in the presence of acetic acid.

4. A process for the production of a resinous product which comprisesreacting one molecular proportion of an N-alkenylarylamine containing analkenyl group of at least 4 carbon atoms and of the general formula:CaHh-l with an equimolecular proportion of a carbonyl compound selectedfrom the group consisting of the aldehydes. and ketones in'the presenceof an acetic acid catalyst.

5. The process otclaim 4 further characterized in that saidR-alkenylarylamine is N-butenylaniline.

6. A process for the production of a resinous product which comprisesreacting one molecular proportion of N-butenylaniline with one molecularproportion of acrolein in the presence of glacial acetic acid to formsaid resinous product.

7. A process for the production of a resinous product which comprisesreacting a carbonyl" compound selected from the group consisting of thealdehydes and ketones with an N-alkenylarylamine containing an alkenylgroup of at least 4 carbon atoms and of the general formula: CaH21l-1and after the resulting action is substantially complete, isolating saidresinous product by mixing the reaction product in water and isolatingthe resin from the resulting aqueous Phase.

8. A resinous material comprising the reaction product of a carbonylcompound selected from the group consisting of the aldehydes and ketoneswith N-butenylaniline.

9. A resinous material comprising the reaction product of a carbonylcompound selected from the group consisting of the aldehydes and ketoneswith an N-alkenylarylamine having an alkenyl group of the generalformula: CaHZn-i and containing at least 4 carbon atoms per group.

10. A process for manufacturing a resinous product which comprisesreacting an aliphatic aldehyde with an N-alkenylarylamine having analkenyl group of at least 4 carbon atoms and of the general formulaCnHLn-i.

11. A process for manufacturing a resinous product which comprisesreacting one molecular proportion of N-butenylaniline with an aldehydein the presence of glacial acetic acid.

12. A process for manufacturing a resinous product which comprisesreacting an N-butenylarylamine with a saturated aliphatic aldehyde.

13. A process for manufacturing a resinous product which comprisesreacting an N-butenylaniline with a saturated aliphatic aldehyde.

14. A process for manufacturing a resinous product which comprisesreacting an N-butenylarylamine with a saturated aliphatic aldehyde inthe presence of an acid condensing agent.

15. A process for manufacturing a resinous product which comprisesreacting an N-butenylaniline witha saturated aliphatic aldehyde in thepresence of an acid condensing agent.

16. A process for preparing a resinous product which comprises reactingan .N-butenylaniline with para-formaldehyde in the presence of glacialacetic acid.

17. A resinous material which comprises the reaction product of anN-butenylarylamine with a saturated aliphatic aldehyde.

18. A resinous material which comprises the reaction product of anN-butenylaniline and a saturated aliphatic aldehyde.

19. A resinous material which comprises the reaction product of anN-butenylaniline and para-formaldehyde.

20. A resinous material comprising the reaction product of an aldehydewith an N-butenylarylamine.

21.A process for manufacturing a resinous product which comprisesreacting an aldehyde with an N-alkenylarylamine having an alkenyl groupof the general formula CnH2n-l and containing at least four carbonatoms.

22. A resinous material comprising the reaction product of an aldehydewith an N-alkenylarylamine having an alkenyl group of the generalformula cnH-zn-i and containing at least four carbon atoms.

JOSEPH D. DANFOR'I'H.

No references cited.

8. A RESINOUS MATERIAL COMPRISING THE REACTION PRODUCT OF A CARBONYLCOMPOUND SELECTED FROM THE GROUP CONSISTING OF THE ALDEHYDES AND KETONESWITH N-BUTENYLANILINE.